Process of making cement and by-products.



' citizen of the United eras Parana an on ARTHUR c. SPENCER, or wnsnrne'ronr, nisrRrc'r or COLUMBIA.

PROCESS OF MAKING CEMENT AND BY-PRODUCTS.

No Drawing.

To all whom it may concern:

Be it known that I, ARTHUR C. SPENCER, a States, residing at Washington, in the District of Columbia, have invented certain new and useful Improvements in Processes of Making Cement and By-Products, of which the following is a specification. v

This invention relates to processes of making cement and byproducts; and it comprises a method of making Portland cement clinker and recovering alkalis wherein a mixture composed of a rock carrying feldspathoid minerals, such as leucite, nephelite' and the like, and the correct proportion of added limestone, or similar form of calcium.

carbonate, to make a mixture having alumina, silica and lime in the correct ratio for Portland cement, is heated insuch a manner as to fume ofi alkali, such alkali being recovered, and is finally converted into cement clinker; and it comprises, as a new compositionof matter, a cement mix comprising comminuted rock carrying substantial proportions or leucite or ,nephelite, or

' both, and limestone in proportions suitable to give Portland cement clinker; all as more fully hereinafter set forthand as claimed.

Inthe manufacture of Portland cement clinker from ordinary clay and limestone, shale and limestone, argillaceous limestones or cement rock, etc., difliculties are presented by the fact that the silica of the mixture is never all in the combined state. Under theconditions prevailing in the rotary cement kiln, While silica in the form of silicates readily combines with lime, the same is not the case with free silica; that is,.silica' in the form of quartz or sand. Free silica combines with lime less easily as compared with silica already in astateof combination. l/vith the usual mixtures therefore,

there 1s' always the risk of leaving some of the silica which may bedesired in the mix ture in the uncombined state where it func= I and the like) I use to furnish the s1l1ca and tions merely as sand, and at the Same'time of producing cement of incorrect composi- Specification of Letters Patent, ]P'a;i;entgdl D9 119 1916, Application filed May 18, 1912. Serial No. 698,192. I

silica present in the uncombined state, and.

furthermore the ratio of silica to alumina is unduly high. I

For most purposes, clays, slates and shales,

taking free and combined silica together,-

may be said to have the composition of granite or gneiss minus a considerable proportion of the alkalis. largely produced by the weathering of common feldspar, a mineral which, in an unweathered and undecomposed state, is a frequent component. As regards the ratio of silica to alumina, this is at least equal to that in feldspar (orthoclase) and is ordi narily much higher, being the higher the more of the quartz of the original rock remains as sand in admixture with the clay. However, assuming that the silica-alumina 'ratio is no higher than that of orthoclase,

this is still too high for cement clinker of the type usually desired, the percentage of silica divided by the percentage of alumina giving av quotient greater than 3. And, as stated, in the'clay much of this silica is in the free state.

In the present invention, I have devised a method of making clinker which obviates the foregoing difliculties. Inlieu ofsecuring the alumina and silica necessary for Portland cement from clays and slates which, as pointed out, are relatively high in silica and invariably contain free silica (sand alumina certain rocks of the type which is now called feldspathoid by geologists and mineralogists, these rocks being characterized by the presence of the feldspathoid minerals, leucite, nephelite and the like. The

They are, or have been feldspathoid minerals (Introduction to M inemlogy, WV. B. Scott, 1898,, page 17) are closely related to the feldspars but differ in crystalline form. They do not contain the excess of silica characterizing the feldspars.

' Unlike thefelds pars, the feldspathoid mill erals are not commonly. found in rocks or rocky materials carrying an excess of free silica; and this is recognized as the difierentiating line between the two classes of rocks. A rock characterized by the. occurrence therein of feldspathoid minerals does not contain free silica.

I Furthermore the feldspathoid minerals, such 33181101178, nephelite' and the'like, diflfer from the potash feldspars in that the latter contain at least and characterized by their presence, are of the same general composition and they normally carry no free silica.

I have discovered that by making a suitable mixture of a finely comminutedrock carrying feldspathoid minerals with limestone, the two being in the correct propor tions to. give the silicazaluminazlime ratio.

of Portland cement, I can produce a good and uniform clinker, attaining certain ad-i vantages. in'the operation without encountering-the complications and exercising the care necessary in using shale and slate. In-

cidentally, moreover, I can pay much of the cost of operation by the recovery of the potash which may be, fumed ofi in preparing ,the cement. In rocks carrying leucite, the

ratio of silica to alumina is ordinarily such that low alumina, slow setting, cement will result from their use; and both alumina and 's'ilicabeing in chemical union in the, rock and in the presence also of a lkalis which have fluxing properties, their transposition to form the characteristic bodies of Portland cement is-ready andeasy. Rocks carrying nephelite, such as nephelite syenite, are relatively rich in alumina and arewelladapted to produce high alumina, quick setting cements, as are rocks carrying leucite. Elther type oi rocks, that is those that contain leucite as acharactcristic constituent; or those carrying nephehte as a characteristic coni stituent, may be used in the present invention. For example, a typical nephelite, syenite,

from Ma et Cove, Ark., ma run 22 per cent. A1 4.5 percent. Fe 8 and 59 per cent. SiO All the silica in this rock is in a vcombmed state, as is the alumina. It will be seen that the. ratio of silica to sesquioxids is not much over 2 :1. This is a 00d ratio for a sound, 1 quick setting Port and cement. Assuming that Portland cement carries 61 per cent. lime, it will be obvious that by ad-' ding the correct proportion of lime'to a rock of th scharacter, the following approxlmate analysis after removing the alkalis will be obtained: SiO 26.8;Al O 10.0; F e 0 2.0; and OaO, 61.',a total of 99.8. This is a good Portland cement clinker.

Apart from the fact that these nephelite rocks furnish silica and alumina (or iron oxid) in combined forms and a good ratio for cement purposes, their use is desirable because of several other considerations. F or one thing, the large amount of alkali present acts as a flux, bringing about a preliminary union and causing a sintering-to take.

.at a low temperature and as the temperature rises the alkalis volatilize and escape while the combinations gradually change to those of cement clinker, ultimately giving a good clinker practically free of alkali. The alkali fumes may conveniently be collected and recovered, giving a valuable byproduct to help pay the'cost of operation. A mixture of nephelite syenite and limestone gives the j greatest amount of. alkali that. can be obtained in a cement mixture from common rocks and at the same time the least amount of uncombined silica; practically none. It also gives the lowest silicazalumina ratio. Taking for comparison a mixture made from pure orthoclase (which is, commercially speaking, a rare material), if proportioned to yield a normal clinker, the cement batch will contain the proportion of 23 .parts SiO 6.8 A1 0,, 6.1 K 0. and 0.2 parts CaO (128 parts limestone). The batch will then'contain 3.7 per cent. alkali. After expelling the K 0, the clinker will contain 23 per cent. SiO 6.8 per cent.

A1 0 and 70.2 per cent. CaO. On the other hand, an averaged analysis of nephelite syenites from Arkansas may give 55.2 SiO 2111- Al,O e.0Fe. -;O 7.43 K 0, "7.46 Na O and'2.00 CaO. 'With this material, to obtain a'clinker carrying the same silica (23 per cent.) only"65..0 parts of lime need be added. The batch will run 4.0 per cent.

' alkali, and the ratio of silica to'se'squioxid in the final clinker instead of being as 23 :6.8, will be as 23:10.4. This heightening o'f'the sesquioxid ratio is valuable in making'sound quick setting cement. Other material of the same sort but; lower in silica content may be used to still further raisejthe percentage of alkali in the raw-mixture, it being possible a to. thus obtain as high as 4.5 per cent. of total potash and soda.

The high proportion of alkali is not only economically important as increasing'the stated, the easy sintering of the mixture and the manufacture of clinker. Its presence suitable for the causes the operation of clinkering to be modified to the extent that a more gradual heating up to the final clinkering temperature is both possible and advisable. The clinker finally obtained contains no important amount of alkali. The rocks I employ'for the present purposes may be any of those containing nephelite minerals as characteristic ingredients, such as nephelite syenite, nephelite basalt, analcite basalt, and the like.

As before stated, leucite and leucite bearing rocks are also suitable materials for the present purposes. A typibal leucite rock may carry. 11 per cent. K 0, 12 per cent. A1 0 7 per cent. Fe O and 56 per cent. silica, the silica being substantially all in combination with the bases. Adding the proper amount of lime in the form of limestone or otherwise to give65 per cent. lime in the clinker, the clinker will have approximately the following analysis: S510 24.5; A1 0 5.5; F6203, 3.0; Ca-O 65.0; total 97.5 per cent; the remainder being accounted for by other constituents present in the raw materials. A cement of this analysis sets somewhat less rapidly than that made from nephelite rocks. Leucite rocks of other'analyses are of course purposes of the presentinvention, the foregoing example being merely typical.

A wide variety of syenites, traps and basalts characterized by the presence of leucitelike minerals or nephelite-like minerals, may be used in the present invention. Where either leucite or nephelite is present in substantialquantities, the rock does not carry mlore than small quantities of uncombined s1 1ca.

Inthe present invention, the rock may be ground or comminuted in any desired way and admixed, with similarly ground limestone, or its equivalents, marl, shells, etc.

The mixture maybe either dry or wet, as in making slurry. It is usually undesira'ble'to admix any proportion of slate or clay with this mixture, though the alkali of the feldspathoid rocks is capable of fiuxing considerable amounts of these materials. The.

mixture may be advanced through an inclined rotary kiln, or a succession of such kilns, (with separate or common firing means) as a thin traveling stream passing under an overlying current of flame and flame gases. Advantageously, the period of exposure to the heat should be rather more prolonged than in the ordinary methods of making cement from slate and the like, but this lengthened exposure should be at arelaitively low temperature. This is for the purpose of thepreliminary sintering" and of fuming off the alkalis, whichgo forward with the kiln dust and-gases and may be collected therefrom in any desired way. This prolongation of the exposure to heat should be at a temperature somewhat below that adopted for ultimate clinkering. One of the advantages of the present invention is that the temperature of clinker formation need not be prolonged in the effort to cause free silica to unite with the bases, but a prolonged exposure to a lower temperature is in no way'disadvantageous; and on theother hand is advantageous both because the alkalis may be economically regained by fuming them olf in this way and because the alkali is thereby removed from the cement. 'As a rule, one part of the rock should be admixed with about 2.5 parts ofsome form of calcium carbonate. The limestone or other form of calcium carbonate used should be reasonably free from magnesia, not containing over five per cent., and should be free from sand and the like.

With material bearing nephelite or leucite containing considerable mica, I have found that a preliminary heating or roasting of the material is a considerable aid to the complete comminution of this flaky mineral constituent. While the rock may be heated alone to a temperature adequate for driving off the constituent water of the mica I have found it to be an advantage to perform this operation after mixing the rock and limestone. A convenient procedure is to crush the batch components, but not to re duce them to powder. The gravelly material is brought to a temperature adequate for calcination of the limestone which is also adequate to dehydrate the mica. The

calcined material is then reduced to a fine powder suitable for the fuming and clinkerlng operations. An advantage of this procedure is that there is av great reduction of the amount of mineral dust in the gases from the clinkering operation, and the alkali fume can thus be readily collected in a purer state than would be otherwise possible. Another procedure sometimes convenient is to crush the materials containing mica and ploy silicious limestone in the batch or to introduce feldspathic material in addition to the nephelite rock and limestone. On the other hand, with leucite rocks having an unusually high silica:alumina ratio, aluminous materials'may be added to the batch to reduce the ratio. v a The dust or fumiform products of the furnace or kiln may be taken up in suspension by the gases which pass therethrough. These products may be collected by means of aflue and passed through settling chambers 5 or dust catchers which may be of any convenient type. It is advantageous to provide water cooled surfaces within the chambers to promote the desired settlingof the pot-' assiferous fume. Of course gas Washers of different types may be employed to efl'ect the, separation of the potash roduct from the gases which carry it out of the kiln.

I do not describe apparatus for carrying out my process as it is suflici'ently obvious that many types of furnaces or kilns maybe adapted for the treatment here described Ifcertain types of kilns are used, it will be I necessary to form the materials of the batch into briquets prior to the heat treatment,

but this procedure which, for reasons stated,

is little advantageous, cannot constitute a departure 'from my invention'which resides in the advantageous constitution of the charge-batch, permitting evolution of alkali at a relatively low temperature, reducing the required consumption of fuel," and. permitting the ready collection of the alkali products.

In Working the mixture ina rotary kiln it is advisable to have the gases leave the kiln at a temperature above, say, 500 0.,

and remain around this temperature for some time since the alkali fume will then remain in suspension after a good part of the coarser batch-dust has settled out. The

alkali-fume thus becomesmore concentrated and on losing'heat condenses so that itmay be precipitated and recovered as a richer product than is possible wherealower temkiln exit. may be readily maintained in working with a. singlekiln it isobvious'that a double kiln setting offers certain advantages in the Way of enablin a close control of thet'empera any of these ways is collected in thefusual manner, cooled, ground and convertedintov cement of commercial grade. It is sometimes advantageous to perform the operation of clinkering: in, 'a mannercalculated' to expel potash more completely than soda. This can be readily accom- .'presence of lime, potash is more readily dissociated-lfrom silicate combinationthan is jsodaf The latter" alkali forms various silicate compounds in' company with lime similar association. 7

7 What I claim is': I I

'1. In the manufacture. of cement clinker and byproducts, the process which comprises making a mixture? cement-formingprofine-grinding, heating to "fume off. alkalis "and converting the "residue into cement and byproducts, the process which comprises p'erature is attained at or just beyond the While the desirable temperature and of- ,comminuted nephelite syenite, pass- I the heat to' form cement clinker." r phshed smce at high temperatures, in the :Whereas potash does not readily. enter into as... comprising comminuted limestone with comminuted rock carrying nepheliteminerals and havinga lowerjratio of s1l1ca I to alumina than characterizes orthoclase.

2.v In the manufacture" of cement. clinker and byproducts, the process which comprises making a mixture-in. cement-formmg proportions comprising. comminuted limestone and comminuted rock carrying. nephelite minerals'a-nd having alower ratio of silica to alumina than characterizes orthoclase, heating said mixture to fume .oif alkalis and converting the residue 'into cement clinker. 3. In the manufacture of cement clinker and byproducts, the process which comprises making an alkali-rich mixture adapted to form cement clinker and comprising comminuted limestone'and comminuted nephelite-bearing rock, passing the same through a rotary kllIl against flame andiflam'e gases till a desired proportionof alkalis is .re-j moved and then raising the heat' to form cement clinker.

4. In the manufacture of 'cement clinkerand byproducts, the process which-comprises making a mixture comprising eement-forming proportions'of a comminuted rock carrying nephelite minerals and mica with granulated limestone, roasting 'the: mixture to calcine the lime and dehydrate the mica,

clinker. I 1 p 5. In the manufacture of cement'clinker making' -a -m1xture 1n cement-forming proportions comprising comminuted limestone with comminuted nephelite sye'nite.

- 6. In the manufacture of cement clinker and byproducts, the process whichcomprises making a mixture m'cement-formingproportions comprising comminuted limestone and comminuted nephelitesyenite, heating said mixture to fume-101i; alkalis andv con- I 'verting the residue into cement clinker. ture at WhlCh the fume-bearing gases make their exit. The cement clinker produced in.

'7. In the'manufacture'of cement clinker and byproducts, the. process which comprises making. a mixture in cement-forming pro-* portions comprising comminuted limestone,

ing thesame through arotar'y kilnfagainst flame and flame. gases till a-desiredpropor- .tion of alkalis'isxremoved and then raising 8. In themanufactureof cement clinker 12 0 and byproducts, the process which compri making a mixture 1n cement-forming'-'pro-1 portions comprising a nephelitefsyenite and mica .with; granulated j'l1m'estone, roasting the .mixtu'retocalcine i'the lime, land dehy- 12 5 drate the mica-, fine-grindirig,fheating to v funi 3 'ofif alkalisj" and converting the residue;

into, cement f' I 9. Asa new composition of. ture oi comminuted rock carrying nephelite minerals and having a lower'ratio of silica to alumina than characterizes orthoclase.

With comminuted limestone, said mixture being in proportions to give a cement clinker.

10. As a new composition of matter, a mixture of commmuted nephellte syemte with comminuted limestone, saidmixture beingin proportions to give a cement clinker. v

11. In the manufacture of cement clinker and byproducts, the process which comprises making an alkali-rich mixture adapted to form cement clinker and comprising comminuted rock carrying feldspathoid min erals and comminuted limestone.

12. In the manufacture of cement clinker and byproducts, the process which comprises making a mixture in cement-forming proportions comprising comminuted limestone and comminuted rock carrying feldspathoid minerals and having a lower ratio of silica to alumina than characterizes orthoclase, heating said mixture to fume off alkalis and converting the residue into' cement clinker.

'13. In the manufacture of cement clinker I and byproducts, the process which comprises maln'ng a mixture 1n cement-forming proportions comprising comminuted limestone 'nuted limestone, said mixture being in proportions to g1ve a cement clinker.

15. The process of making cement clinker which comprises mixing with basiccalcareous material natural silicate material of the feldspathoid type containin alumina and substantially free of uncom ined silica or uncombined alumina and having a lower ratio of silica to alumina than characterizes orthoclase, and clinkering the mixture.

In testimony whereof, I affix my signature in the presence of two subscribing witnesses.

ARTHUR C. SPENCER.

Witnesses:

K. P. MoELRoY, R. F. STEWARD. 

